CN117623281A - Method for preparing curved carbon nanobelt by catalyzing and removing HCl through Pd - Google Patents
Method for preparing curved carbon nanobelt by catalyzing and removing HCl through Pd Download PDFInfo
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- CN117623281A CN117623281A CN202311698632.5A CN202311698632A CN117623281A CN 117623281 A CN117623281 A CN 117623281A CN 202311698632 A CN202311698632 A CN 202311698632A CN 117623281 A CN117623281 A CN 117623281A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002127 nanobelt Substances 0.000 title abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 105
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002074 nanoribbon Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005694 sulfonylation reaction Methods 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- WMKGGPCROCCUDY-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one Chemical compound C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WMKGGPCROCCUDY-UHFFFAOYSA-N 0.000 claims description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical group C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 abstract description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 8
- 239000002109 single walled nanotube Substances 0.000 abstract description 7
- 150000001923 cyclic compounds Chemical class 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 150000002366 halogen compounds Chemical class 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 19
- 239000012043 crude product Substances 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- -1 di-tert-butylmethylphosphonium tetrafluoroborate Chemical compound 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 241000235648 Pichia Species 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002063 nanoring Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001894 space-charge-limited current method Methods 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 description 1
- GAQKEAQMVDKCAF-UHFFFAOYSA-N 1-bromo-2-chloro-4-iodobenzene Chemical compound ClC1=CC(I)=CC=C1Br GAQKEAQMVDKCAF-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VLGSRJCUNKGJCE-UHFFFAOYSA-N boric acid 1,3,5-trimethylbenzene Chemical compound B(O)(O)O.CC1=CC(=CC(=C1)C)C VLGSRJCUNKGJCE-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a curved carbon nanobelt by catalyzing and removing HCl by Pd, wherein the structure of the curved carbon nanobelt is schematically shown as follows:wherein R is hydrogen, C 1‑20 Alkyl, C 1‑20 Alkoxy, mesityl, phenyl or a large pi-extending derivative thereof, n being 1 or 3. The product prepared by the method of the invention can be regarded as a side wall segment of the (m, m) carbon nanotube. The invention adopts a compound with borate groups to carry out Suzuki-Miyaura cross coupling reaction and reduction aromatization reaction with a halogen compound to obtain a carbon nano cyclic compound, and then obtains armchair-type carbon nanobelts with different sizes after further Suzuki-Miyaura cross coupling reaction and Pd catalysis HCl removal. The synthesis method is unique, novel in structure, good in photophysical property and potential in growing single-wall carbon nanotubes from bottom to top.
Description
Technical Field
The invention belongs to the technical field of organic materials, and particularly relates to a method for preparing a curved carbon nanobelt by catalyzing and removing HCl by Pd.
Background
Since the discovery and detailed resolution of Carbon Nanotube (CNTs) structures by Iijima in 1991 1 Has been paid great attention to due to its outstanding mechanical, electrical and optical properties, and has been successfully used as an electric field emission material, a battery, a scanning electron microscope probe, a chemical sensor, a hydrogen storage material, etc 2-4 . However, the conventional method for preparing carbon nanotubesThere are still many limitations such as a disordered structure, a series of CNTs of different length, diameter and chirality, and high separation cost, which is not suitable for mass production 5-6 . Thus, in the last few years, bottom-up synthesis has become a promising strategy for synthesis, drawing a great deal of attention in exploring different types of bends or cyclic structures.
In 2008, jastin group synthesized ring para-phenylene (CPPs) as the first repeating unit for cross-cutting armchair-type carbon nanotube with definite diameter and chirality for the first time 7 . Ilami study group thereafter 8 ，Yamago 9 The research groups respectively adopt different synthesis strategies to obtain CNTs transverse cutting units with different diameters and chiralities, which can be called as carbon nano rings.
Carbon Nanoribbons (CNBs) are one type of carbon nanorings, which are closed cyclic compounds composed of fully fused benzene rings, and require cleavage of at least two C-C bonds to break their ring structure 11 . CNBs can be regarded as fused ring sidewall segments of single-walled carbon nanotubes, and thus can be classified into armchairs, saw-tooth, and chiral carbon nanoribbons according to the chiral index (n, m) of single-walled carbon nanotubes (SWCNTs). The CNBs structure not only keeps the important structural information such as the diameter, pitch and the like of the corresponding CNTs, but also is an ideal template for constructing CNTs with uniform structures, and has very interesting photophysical properties such as size quantum effect, supermolecular properties, chirality and the like. And it reveals important concepts of aromaticity, conjugation, and strain, and plays a unique role in bottom-up chiral specific SWCNTs synthesis. In recent years, itami research team 10 Successfully synthesizing a section of (6, 6) carbon nano-belt through iterative Wittig reaction and intramolecular Yamamoto coupling, which is the first time of organic synthesis of a carbon nano-tube segment with an armchair; subsequently, miao team 11 The synthesis of armchair (12, 12) carbon nanotubes and the side wall segments of the first chiral (18, 12) carbon nanotubes by Suzuki coupling, reductive aromatization and Scholl reaction is reported. In 2020, chi and Itam research team independently reported the synthesis of the first saw tooth carbon nanoribbon 12,13 . However, nanoribbon synthesis strategies are severely limited and reportedThe method has low average yield and can not provide material support and experimental support for later functionalization and application.
Reference to the literature
[1]Iijima,S.,Helical Microtubules of Graphitic Carbon.Nature 1991,354(6348),56-58.
[2]Dresselhaus,M.S.；Dresselhaus,G.；Charlier,J.C.；Hernández,E.Electronic,thermal and mechanical properties of carbon nanotubes.Philos.Trans.R.Soc.London,Ser.A2004,362,2065-2098.
[3]Terrones,M.Carbon nanotubes:Synthesis and Properties,Electronic Devices and Other Emerging Applications.Int.Mater.Rev.2013,49,325-377.
[4]Schroeder,V.；Savagatrup,S.；He,M.；Lin,S.；Swager,T.M.Carbon Nanotube Chemical Sensors.Chem.Rev.2019,119,599-663.
[5]Guo,T.；Nikolaev,P.；Thess,A.；Colbert,D.T.；Smalley,R.E.Catalytic growth of single-walled manotubes by laser vaporization.Chem.Phys.Lett.,1995,243,49-54.
[6]José-Yacamán,M.；Miki-Yoshida,M.；Rendón,L.；Santiesteban,J.G.Catalytic growth of carbon microtubules with fullerene structure.Appl.Phys.Lett.,1993,62,657-659.
[7]Jasti,R.；Bhattacharjee,J.；Neaton,J.B.；Bertozzi,C.R.,Synthesis,characterization,and theory of[9]-,[12]-,and[18]cycloparaphenylene:carbon nanohoop structures.J.Am.Chem.Soc.2008,130(52),17646-17647.
[8]Takaba,H.；Omachi,H.；Yamamoto,Y.；Bouffard,J.；Itami,K.,Selective Synthesis of [12]Cycloparaphenylene.Angew.Chem.Int.Ed.2009,48(33),6112-6116.
[9]Yamago,S.；Watanabe,Y.；Iwamoto,T.,Synthesis of[8]cycloparaphenylene from a square-shaped tetranuclear platinum complex.Angew.Chem.Int.Ed.2010,49(4),757-759.
[10]Povie,G.；Segawa,Y.；Nishihara,T.；Miyauchi,Y.；Itami,K.,Synthesis of a carbon nanobelt.Science 2017,356(6334),172-175.
[11]Cheung,K.Y.；Gui,S.；Deng,C.；Liang,H.；Xia,Z.；Liu,Z.；Chi,L.；Miao,Q.,Synthesis of Armchair and Chiral Carbon Nanobelts.Chem 2019,5(4),838-847.
[12]Cheung K.Y.,Watanabe K.,Segawa Y.,Itami K.,Synthesis of a Zigzag Carbon Nanobelt[J].Nat.Chem.,2021,13(3):255-259.
[13]Han Y.,Dong S.Q.,Shao J.W.,Fan W.,Chi C.Y.,Synthesis of a Sidewall Fragment of A(12,0)Carbon Nanotube[J].Angew.Chem.,Int.Ed.,2021,60(5):2658-2662.
Disclosure of Invention
In view of this, the present invention aims to provide a method for preparing curved carbon nanoribbons (or armchair-type carbon nanoribbons) by Pd-catalyzed dehydroHCl. The present invention employs a novel method for preparing armchair-type carbon nanobelts, with which two armchair-type carbon nanobelts can be obtained at a time, such as (12, 12) carbon nanobelts and (16, 16) carbon nanobelts at the same time. The synthesis method is unique, the purification method of the product is simple, the yield is high, the solubility is good, the good photophysical property is shown, and the product is used as a side wall segment of the single-walled carbon nanotube, so that the method has potential application of growing the single-structured single-walled carbon nanotube from bottom to top. In addition, the invention has an organically conjugated pi-extending structure, considering that the carbon nanotubes and the related structures thereof have remarkable electrical properties, can be regarded as side wall segments of (12, 12) and (16, 16) carbon nanotubes, and can be used as electron transport materials of electronic devices.
The invention relates to a curved carbon nano-belt prepared by a novel Pd catalytic HCl removal method, which has the following structure:
wherein R is selected from hydrogen, C 1-20 Alkyl, C 1-20 Alkoxy, mesityl, phenyl or a large pi-extending derivative thereof; n has a value of 1 or 3.
In a preferred embodiment, we exemplify that R is mesityl, n is 1 or 3.
The invention relates to a method for preparing a curved carbon nano-belt by Pd catalytic HCl removal, which comprises the following steps:
step 1: in a mixed solvent, under the existence of a catalyst (10% -30%, the same applies below), a ligand (50% -80%, the same applies below), alkali (12-20, the same applies below) and a phase transfer catalyst (20% -30%), carrying out Suzuki-Miyaura cross-coupling reaction on a compound shown in a formula (II) and a compound shown in a formula (III) (molar ratio 1:1) at a certain temperature, and carrying out reduction aromatization reaction under acidic condition and at room temperature, thereby obtaining a compound shown in a formula (IV);
step 2: in a pure organic solvent, under the condition that the temperature is less than minus 40 ℃, OBn in the structure of the compound shown in the formula (IV) is changed into OH, and sulfonylation reaction is carried out to obtain the compound shown in the formula (V);
step 3: in a mixed solvent, carrying out a Suzuki-Miyaura cross-coupling reaction on a compound shown in a formula (V) and a compound shown in a formula (VI) at a certain temperature in the presence of a catalyst and alkali to obtain a compound shown in a formula (VII);
step 4: in a pure organic solvent, in the presence of a catalyst, a ligand and alkali, the compound shown in the formula (VII) undergoes intramolecular elimination reaction at a certain temperature to obtain the target product shown in the formula (I).
In the step 1, the catalyst is a palladium catalyst selected from tetra (triphenylphosphine) palladium or tri (dibenzylidene) acetone dipalladium; the ligand is a phosphorus-based ligand such as 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl; the alkali is potassium carbonate or sodium carbonate; the phase transfer catalyst is tetra-n-butyl ammonium bromide.
In the step 1, the mixed solvent is formed by compounding toluene and water, and the proportion is 10:1 to 25:1, V/V. The acidic conditions are provided by stannic acid prepared from stannous chloride and hydrochloric acid in tetrahydrofuran.
In the step 1, the reaction temperature of the Suzuki-Miyaura cross-coupling reaction is 60-120 ℃ and the reaction time is 1-5 days.
In step 2, the OBn group has the structure ofThe reagent used for the conversion to OH was a solution of boron trichloride or boron tribromide in methylene chloride, and the reaction time was 9 hours.
In step 2, the reagents used in the sulfonylation reaction were dried pyridine and trifluoromethanesulfonic anhydride, and the reaction time was 12 hours.
In step 2, the pure organic solvent is dried dichloromethane.
In the step 3, the catalyst is tetraphenylphosphine palladium; the alkali is potassium carbonate or sodium carbonate; the mixed solvent is toluene and water; the reaction temperature is 60-120 ℃ and the reaction time is 1-5 days.
In step 4, the catalyst is a palladium catalyst, such as palladium acetate or palladium dichloride; the ligand is a phosphorus-based ligand such as di-tert-butylmethylphosphonium tetrafluoroborate or tricyclohexylphosphine; the base is 1, 8-diazabicyclo undec-7-ene (DBU), cesium carbonate or 2, 2-dimethylpropionic acid; the pure organic solvent is dry N, N-dimethylacetamide; the reaction temperature is 60-120 ℃ and the reaction time is 1-5 days.
In the step 4, the reaction vessel used in the reaction process is a coated explosion-proof thick-wall pressure-resistant bottle.
The reactions of steps 1-4 were carried out under argon or nitrogen atmosphere.
The synthesis route of the armchair type carbon nano belt material is as follows:
wherein R is 1 Is a boric acid group or a boric acid ester group, R is hydrogen, C 1-20 Alkyl, C 1-20 Alkoxy, mesityl, phenyl or a large pi-extending derivative thereof, n being 1 or 3.
Compared with the prior art, the invention has the beneficial effects that:
1. the method for catalyzing and removing HCl by Pd is adopted for the first time in the experimental method to prepare the curved carbon nano-belt structure;
2. two macrocyclic precursors with different sizes can be obtained through one-step reaction (step 1), and then two carbon nanobelts with different sizes can be obtained;
3. the synthesis steps of the invention are simple, convenient and efficient, and the two raw material molecules are easy and rapid to prepare in large quantities, and the synthesis steps are short and the operation is convenient;
4. the precursor molecules used are easy to functionalize, i.e. the substituent R of the precursor molecules is easy to change, and the structures of target products can be rapidly enriched, for example, different conjugated extension degrees and the like of the target products are changed, so that the target products show different physical properties.
Drawings
FIG. 1 is an ultraviolet-visible (UV-Vis) (curve) and fluorescence spectrum (FL) spectrum (solid line) of the structure of formula (VII) in Dichloromethane (DCM) provided in example 1 of the present invention;
FIG. 2 is a chart showing the fluorescence decay lifetime test spectrum of the structure of formula (VII) in Dichloromethane (DCM) provided in example 1 of the present invention;
FIG. 3 shows a matrix assisted laser desorption tandem time of flight mass spectrometry (MALDI-TOF-MS) spectrum (solid line) and simulated data (dotted line) of the structure of formula (I) provided in example 1 of the present invention;
FIG. 4 shows the structure of formula (I) in deuterated chloroform (CDCl) as provided in example 1 of the present invention 3 ) Nuclear magnetic resonance hydrogen spectrum [ ] 1 H NMR) spectrum;
FIG. 5 is an ultraviolet-visible (UV-Vis) (curve) and fluorescence spectrum (FL) spectrum (solid line) of the structure of formula (I) in Dichloromethane (DCM) provided in example 1 of the present invention;
FIG. 6 is a chart of a fluorescence decay lifetime test spectrum at 436nm of the structure of formula (I) in Dichloromethane (DCM) provided in example 1 of the present invention;
FIG. 7 is a graph of fluorescence decay lifetime test spectrum at 464nm of structure of formula (I) in Dichloromethane (DCM) as provided in example 1 of the present invention.
FIG. 8 shows a J of an ITO/ZnO/I/Ca/Al electron transport device constructed in the structure of formula (I, CPP16-16 (ph-Mes)) provided in example 1 of the present invention 1/2 -V fitting a graph showing its application to electron transport properties in a carrier transport device.
Detailed Description
The invention relates to a method for preparing a curved carbon nano-belt material by Pd catalytic HCl removal, which comprises the following synthetic route:
wherein R is 1 Is a boric acid group or a boric acid ester group, R is hydrogen, C 1-20 Alkyl, C 1-20 Alkoxy, mesityl, phenyl or a large pi-extending derivative thereof, n being 1 or 3.
In the present invention, C 1-20 The alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl and the like.
In the present invention, C 1-20 The alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexoxy, isohexoxy, etc.
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1: synthesis of armchair-type carbon nanobelts having the structure of formula (I) (wherein R 1 Is pinacol borate, R is mesityl, n is 3)
1. Synthesis of structure (n is 3) of formula (iv): 844mg of a compound of formula (II) (wherein R 1 As pinacol borate groups, this compound is synthesized by the article Angew.chem.int.ed.2021,60,17368-17372 using 1, 4-dibromobenzene available from Enoki Corp.) 500mg of a compound of formula (III) (this compound is described by the article org.biomol.chem2005,3,524-537, the starting material hydroquinone used was purchased from enokie, 108mg tetra (n-butyl) ammonium bromide, 138mg 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl and 153mg of dibenzylideneacetone dipalladium were added to a mixed solvent of toluene (250 mL) and water (25 mL). The mixture was bubbled with argon for 25 minutes, then the flask was sealed and heated to 85 ℃ for 5 days. After the reaction was completed, the above reaction mixture was cooled to room temperature, toluene as a solvent was dried by spin-drying using a rotary evaporator (available from Shanghai Yikai Instrument Co., ltd., hereinafter the same) and then extracted with methylene chloride (3X 100 mL), the organic phases were combined, washed twice with brine, dried over anhydrous magnesium sulfate and dried by spin-drying using a rotary evaporator, and the obtained crude product was evacuated in a vacuum oven for 4 hours. During this period, 1.631g of stannous chloride dihydrate was placed in a 250mL flask equipped with a magnetic stirring device, 150mL of tetrahydrofuran was added, bubbling with argon for 15 minutes, and then 1.2mL of concentrated hydrochloric acid was added to react for more than 30 minutes to obtain stannic acid. The dried crude product was then degassed by pumping vacuum through an oil pump and backfilling with argon for 3 cycles, and the prepared stannic acid was injected into the crude product and reacted overnight at room temperature. After the reaction, the solvent tetrahydrofuran was dried by spin-drying using a rotary evaporator, then extracted with dichloromethane (3×100 mL), the organic phases were combined, washed twice with brine, dried over anhydrous magnesium sulfate, and dried by spin-drying using a rotary evaporator, and the crude product obtained was preliminarily purified on a silica gel column using petroleum ether and dichloromethane (volume ratio of 1:1) as eluent, and recrystallized using pure methanol to give an off-white product, i.e., the compound of formula (iv) having the structure (n is 3) in 103mg (3.2%) yield.
The resulting compound of formula (IV) (n is 3) was characterized by using a matrix assisted laser desorption time of flight (MALDI-TOF) tandem mass spectrometer (model: autoflex Speed TOF/TOF, manufacturer: brookfield, USA, supra): theoretical m/z value: 2913.1789, experimental values: 2913.7449. and was also characterized by nuclear magnetic resonance hydrogen spectroscopy (model: bruker AVANCE AV400, manufacturer: bruker, switzerland, supra): 1 H NMR(400MHz,CDCl 3 ):δ7.64(s,32H),7.30-7.33(m,80H),7.07(s,16H),5.01(s,32H)。
2. synthesis of structure (n is 3) of formula (v): 80mg of the compound of formula (IV) (n is 4), 412mg of 1,2,4, 5-tetramethylbenzene is placed in a 150mL flask equipped with a magnetic stirring apparatus, 50mL of anhydrous methylene chloride is added thereto, bubbling with argon for 15 minutes, and then placed in an ethanol bath at-78℃for 30 minutes, followed by 1.2mL of a 1M methylene chloride solution of boron trichloride. After 9 hours of reaction, the reaction flask was quenched with 0.7mL of methanol, then extracted with water, the organic layer was separated, the aqueous layer was further extracted with diethyl ether (3X 25 mL), the organic phases were combined, and the organic phase was quenched with anhydrous Na 2 SO 4 Drying and filtering to remove Na 2 SO 4 After that, the solvent was spin-dried with a rotary evaporator to give a crude product, which was used directly in the next step without further purification. 50mL of anhydrous methylene chloride was added to the above crude product, bubbling with argon gas under an ice-water bath for 15 minutes, then 0.9mL of anhydrous pyridine was added, after 5 seconds, 0.8mL of trifluoromethanesulfonic anhydride was added, and then the reaction was allowed to warm to room temperature and reacted for 12 hours or more. After completion of the reaction, 40mL of 1mol/L HCl solution was added to the reaction mixture, followed by extraction with methylene chloride (3X 40 mL), and the organic phases were combined, washed twice with brine, and then with anhydrous Na 2 SO 4 And (5) drying. The crude product was purified by column chromatography on silica gel using petroleum ether and dichloromethane (1:1 by volume). Recrystallisation with pure methanol gives the product as a white solid, i.e. the compound of formula (V) with a structure (n is 3) in 61mg (62%).
The resulting compound of formula (v) (n is 3) is characterized by nuclear magnetic resonance hydrogen spectroscopy: 1 HNMR(400MHz,CDCl 3 ):δ7.65(d,J＝9.4Hz,32H),7.51(d,J＝16.6Hz,16H)。
3. synthesis of structure (R is mesityl) of formula (vi): in a 100mL flask equipped with a magnetic stirring device, 2g of 1-bromo-2-chloro-4-iodobenzene (purchased from Pichia), 1.03g of mesitylene boric acid (purchased from Pichia), 1.3g of potassium carbonate and 72.8mg of tetrakis (triphenylphosphine) palladium were added to a mixed solvent of tetrahydrofuran (30 mL) and water (6 mL) were placed in a bottle, the mixture was bubbled with argon for 15 minutes, and then the flask was sealed and heated to 75℃for 48 hours of reaction. After the reaction was completed, the solvent was dried by spin-drying with a rotary evaporator, extracted with dichloromethane (3×50 mL), the organic phases were combined, washed twice with brine, and dried with anhydrous sodium sulfate, and the obtained crude product was purified on a silica gel column using petroleum ether as eluent to obtain a colorless transparent oil, which was precursor 4' -bromo-3 ' -chloro-2, 4, 6-trimethyl-1, 1' -biphenyl of the structure (R is mesitylene) of formula (vi), 1.86g (95.3%) was produced, characterized by nuclear magnetic resonance hydrogen spectrum: 1 H NMR(400MHz,CDCl 3 ) Delta 7.63 (dd, J=8.2, 1.0Hz, 1H), 7.28-7.24 (m, 1H), 6.96-6.92 (m, 2H), 6.91-6.87 (m, 1H), 2.32 (d, J=1.3 Hz, 3H), 2.01 (d, J=1.6 Hz, 6H). Then, 1.8g of 4' -bromo-3 ' -chloro-2, 4, 6-trimethyl-1, 1' -biphenyl was placed in a 100mL flask equipped with a magnetic stirring device, the above mixture was degassed by pumping vacuum and backfilling with argon for 3 cycles, and 30mL of anhydrous tetrahydrofuran was added thereto, placed in an ethanol bath at-78℃for 30 minutes, then 3.5mL of a 2.5M n-hexane solution of n-butyllithium was added dropwise, and after 2 hours of reaction, 2.2mL of trimethyl borate was added dropwise. The reaction was continued for 2 hours and then gradually warmed to room temperature for more than 10 hours. Then, 20mL of 1M HCl solution was added to the flask and stirred for 1 hour or more. Tetrahydrofuran was then removed by rotary evaporation, extracted with dichloromethane (3X 50 mL), the organic phases combined and dried over anhydrous sodium sulfate, and the crude product obtained was washed with petroleum ether to yield a white solid, i.e., the compound of formula (VI) in which R is mesitylene, in a yield of 1.53g (95.8%).
The resulting compound of formula (vi) (R is mesityl) is characterized by nuclear magnetic resonance hydrogen spectroscopy: 1 HNMR(400MHz,CDCl 3 ):δ8.00(d,J＝7.6Hz,1H),7.17(d,J＝1.5Hz,1H),7.12(dd,J＝7.7,1.5Hz,1H),6.94(s,2H),5.50(s,2H),2.33(s,3H),2.00(s,6H)。
4. synthesis of Structure (VII) (R is mesityl and n is 3): in a 25mL flask equipped with a magnetic stirring device, 150mg of the compound of formula (V) (n is 3), 330mg of the compound of formula (VI) (R is mesityl), 550mg of potassium carbonate and 10mg of tetrakis (triphenylphosphine) palladium were added to a mixed solvent of toluene (10 mL) and water (2 mL), placed in a bottle, the mixture was bubbled with argon for 20 minutes, and then the flask was sealed and heated to 110℃for 48 hours. After the reaction was completed, the solvent was dried by spin-drying with a rotary evaporator, extracted with methylene chloride (3×30 mL), the organic phases were combined, and dried over anhydrous sodium sulfate, and the obtained crude product was purified on a silica gel column using petroleum ether and methylene chloride (volume ratio of 2:1) as eluent (visible blue fluorescence was observed on the silica gel column with a 365nm fluorescent lamp), and then washed three times with methanol to obtain a white solid product in 128mg (62.7%).
The resulting compound of formula (vii) (R is mesityl and n is 3) was characterized by using a matrix assisted laser desorption time of flight (MALDI-TOF) tandem mass spectrometer: theoretical m/z value: 4876.6283, experimental values: 4876.6524. and characterized by nuclear magnetic resonance hydrogen spectroscopy: 1 H NMR(400MHz,CDCl 3 ) Delta 7.41 (s, 16H), 7.10 (s, 32H), 7.05 (d, J=6.5 Hz, 32H), 6.83 (s, 48H), 2.20 (s, 48H), 1.98 (s, 96H). Characterization was performed by ultraviolet-visible (model: UV-3802, manufacturer: china You Nike (Shanghai) instruments Co.) and fluorescence spectroscopy (model: fluoMax-4, manufacturer: horba group, japan): UV-Vis (DCM solution) produces an absorption signal in the range of about 250-650nm, with larger absorption peaks predominantly at 264nm and 317 nm; FL (DCM solution) produces an emission signal approximately in the 340-660nm range with a maximum emission peak at 415nm, see FIG. 1; fluorescence decay lifetime tests were performed using a fluorescence lifetime spectrometer (model: mini-Tau, manufacturer: tianmei Instrument Tuo laboratory Equipment (Shanghai) Co., ltd.) whose lifetime (τ) exhibits a single exponential characteristic decay at an excitation wavelength of 415nm, the fluorescence lifetime value can be determined to τ=1.18 ns, see FIG. 2.
5. Synthesis of Structure (R is mesityl and n is 3) of formula (I): 20mg of the compound of formula (VII) (R is mesityl, N is 3), 1.7mg of palladium dichloride bis (tricyclohexylphosphine), 0.5mg of 2, 2-dimethylpropionic acid and 47mg of cesium carbonate are added to 3mL of super-dry N, N-dimethylacetamide, and the mixture is placed in a 15mL film-coated explosion-proof thick-wall pressure-resistant bottle, the mixture is bubbled with argon for 20 minutes, and then the pressure-resistant bottle is sealed and heated to 150 ℃ for reaction for 3 to 5 days. After the reaction was completed, the organic phases were directly extracted with methylene chloride (3×30 mL), combined and dried over anhydrous sodium sulfate, and the obtained crude product was purified on a silica gel column using petroleum ether and methylene chloride (volume ratio: 1:1) as eluent (visible blue-green fluorescence was observed on the silica gel column with a 365nm fluorescent lamp), and then washed three times with methanol to obtain a yellowish green solid product in a yield of 7mg (39.8%).
The resulting compound of formula (i) (R is mesityl and n is 3) is characterized by using a matrix assisted laser desorption time of flight (MALDI-TOF) tandem mass spectrometer: theoretical m/z value: 4292.9833, experimental values: 4292.9114, see fig. 3. And characterized by nuclear magnetic resonance hydrogen spectroscopy: 1 H NMR(400MHz,CDCl 3 ) Delta 9.69 (s, 32H), 8.93 (s, 16H), 8.65 (s, 16H), 7.61 (s, 16H), 7.11 (s, 32H), 2.45 (s, 48H), 2.34.1.91 (m, 96H) are shown in FIG. 4. Characterization was performed by ultraviolet-visible (model: UV-3802, manufacturer: china You Nike (Shanghai) instruments Co.) and fluorescence spectroscopy (model: fluoMax-4, manufacturer: horba group, japan): UV-Vis (DCM solution) produces an absorption signal in the approximate range of 250-650nm, with the larger absorption peaks predominantly at 287nm, 341nm, 394nm and 421 nm; FL (DCM solution) produces an emission signal approximately in the 340-660nm range, with maximum emission peaks at 436nm and 464nm, see FIG. 5. Fluorescence decay lifetime test was performed using a fluorescence lifetime spectrometer (model: mini-Tau, manufacturer: tianmei Instrument Tuo laboratory Equipment (Shanghai) Co., ltd.) whose lifetime (τ) showed a single exponential characteristic decay at 436nm excitation wavelength, and the fluorescence lifetime value could be determined as τ 1 =2.29 ns, see fig. 6, also exhibiting a single exponential decay at 464nm excitation wavelength, the fluorescence lifetime value can be determined as τ 2 =2.35 ns, see fig. 7. Its electron mobility was tested by the space charge limited current model (SCLC method). Using (I) as an electron transport layer, and forming a pure electronic transport device by ITO/ZnO/I/Ca/Al; the electron mobility was calculated to be about 2.7X10 using the Mott-Gunney equation -4 cm 2 V -1 s -1 See fig. 8.
Example 2: synthesis of armchair-type carbon nanobelts having the structure of formula (I) (wherein R 1 Is pinacol borate, R is mesitylN is 1
1. Synthesis of structure (n is 1) of formula (iv): the crude product obtained in example 1 was initially purified on a silica gel column using petroleum ether and methylene chloride (volume ratio 3:1) as eluent, and recrystallized from pure methanol to give the yellowish green product, i.e. the compound of formula (IV) with structure (n: 1), yield 542mg (16.8%). The rest of the procedure is the same as in example 1.
2. Synthesis of structure (n is 1) of formula (v): the procedure was as in example 1. The crude product obtained was purified by column chromatography on silica gel using petroleum ether and dichloromethane (volume ratio 2:1) as eluent. Recrystallisation with pure methanol gives the product as a white solid, i.e. the compound of formula (V) with structure (n is 1) in 32mg (35%).
3. Synthesis of structure (R is mesityl) of formula (vi): the procedure was as in example 1.
4. Synthesis of Structure (VII) (R is mesityl and n is 1): the procedure was as in example 1. The difference is that the crude product obtained is purified on a silica gel column with petroleum ether and methylene chloride (volume ratio 3:1) as eluent.
5. Synthesis of Structure (R is mesityl, n is 1) of formula (I): the procedure was as in example 1. The difference is that the crude product obtained is purified on a silica gel column with petroleum ether and methylene chloride (volume ratio 2:1) as eluents (visible yellow-green fluorescence is visible on the silica gel column with a 365nm fluorescent lamp).
Claims (9)
1. A method for preparing a curved carbon nanoribbon by Pd catalytic HCl removal, which is characterized by comprising the following steps:
step 1: in a mixed solvent, carrying out Suzuki-Miyaura cross-coupling reaction on a compound shown in a formula (II) and a compound shown in a formula (III) in the presence of a catalyst, a ligand, a base and a phase transfer catalyst, and carrying out reduction aromatization reaction under acidic conditions and at room temperature to obtain a compound shown in a formula (IV);
step 2: in a pure organic solvent, under the condition that the temperature is less than minus 40 ℃, OBn in the structure of the compound shown in the formula (IV) is changed into OH, and sulfonylation reaction is carried out to obtain the compound shown in the formula (V);
step 3: in a mixed solvent, carrying out a Suzuki-Miyaura cross-coupling reaction on a compound shown in a formula (V) and a compound shown in a formula (VI) at a certain temperature in the presence of a catalyst and alkali to obtain a compound shown in a formula (VII);
step 4: in a pure organic solvent, in the presence of a catalyst, a ligand and alkali, carrying out intramolecular elimination reaction on a compound shown in a formula (VII) at a certain temperature to obtain a target product shown in a formula (I);
the synthetic route is as follows:
wherein R is 1 Is a boric acid group or a boric acid ester group, R is hydrogen, C 1-20 Alkyl, C 1-20 Alkoxy, mesityl, phenyl or a large pi-extending derivative thereof, n being 1 or 3.
2. The method according to claim 1, characterized in that:
in the step 1, the catalyst is a palladium catalyst selected from tetra (triphenylphosphine) palladium or tri (dibenzylidene) acetone dipalladium; the ligand is a phosphorus-based ligand; the alkali is potassium carbonate or sodium carbonate; the phase transfer catalyst is tetra-n-butyl ammonium bromide.
3. The method according to claim 2, characterized in that:
in the step 1, the ligand is 2-dicyclohexylphosphine-2 ',6' -dimethoxy biphenyl.
4. The method according to claim 1, characterized in that:
in the step 1, the mixed solvent is formed by compounding toluene and water; the acidic conditions are provided by stannic acid prepared from stannous chloride and hydrochloric acid in tetrahydrofuran.
5. The method according to claim 1, characterized in that:
in the step 1, the reaction temperature of the Suzuki-Miyaura cross-coupling reaction is 60-120 ℃ and the reaction time is 1-5 days.
6. The method according to claim 1, characterized in that:
in step 2, the OBn group has the structure ofThe reagent used for the conversion to OH was a solution of boron trichloride or boron tribromide in methylene chloride, and the reaction time was 9 hours.
7. The method according to claim 1, characterized in that:
in the step 3, the catalyst is tetraphenylphosphine palladium; the alkali is potassium carbonate or sodium carbonate; the reaction temperature is 60-120 ℃ and the reaction time is 1-5 days.
8. The method according to claim 1, characterized in that:
in the step 4, the catalyst is a palladium catalyst selected from palladium acetate or palladium dichloride; the ligand is a phosphorus-based ligand; the alkali is 1, 8-diazabicyclo undec-7-ene, cesium carbonate or 2, 2-dimethylpropionic acid; the reaction temperature is 60-120 ℃ and the reaction time is 1-5 days.
9. A curved carbon nanoribbon prepared by the method of any one of claims 1-9, having the structure shown below:
wherein R is selected fromFrom hydrogen, C 1-20 Alkyl, C 1-20 Alkoxy, mesityl, phenyl or a large pi-extending derivative thereof; n has a value of 1 or 3.
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